Bazı meyve ve sebzelerde pestisit kalıntılarının analizinde yüksek basınçlı sıvı kromatografisi (HPLC) ile çoklu kalıntı analiz metodunun geliştirilmesi

Multi-residue analyse method using high-pressure liquid chromatography (HPLC) with Diode Array Detector was investigated for the determination of 19 pesticides. Acetonitrile, anhydrous magnesium sulphate and sodium chloride were used in extraction process via anhydrous magnesium sulphate and primary secondary amine were used in cleanup process. Pesticide free samples of eggplant, peach, tomato, mandarin were used for method validation studies and results were found at acceptable range. Instrument Detection Limit (IDL) and Estimated Method Detection Limit (EMDL) were calculated for each pesticide. Correlation coefficient which were acquired from matrix matched calibration graphs were higher than 0.99. Mean recoveries were between 75.39-121.95% and relative standart deviations (RSD%) were lower than 20% for accuracy. Also the RSD which were calculated for precision (intra-day repeatability and inter-day reproducibility) were found lower than 10%. It is thought that, this method can be used easily for residue monitoring programmes. It is simple, economic and has small waste.

Anahtar Kelimeler:

Çoklu kalıntı analiz metodu, HPLC, pestisit kalıntısı, meyve, sebze

Improvement of multi residue analysis method for pesticide residues in some fruits and vegetables using high pressure liquid chromatography (HPLC)

Yüksek Basınçlı Sıvı Kromatografisi (HPLC)-Diode Array Dedektör kullanılarak 19 tane pestisitin kalıntı analizine imkan sağlayan çoklu kalıntı analiz metodu geliştirilmiştir. Ekstraksiyon işleminde asetonitril, susuz magnezyum sülfat ve sodyum klorür ile temizleme işleminde susuz magnezyum sülfat ve primer sekonder amin kullanılmıştır. Metot geçerli kılma çalışmalarında pestisit içermeyen patlıcan, şeftali, domates, mandalina örnekleri kullanılmış ve sonuçlar kabul edilebilir aralıklarda bulunmuştur. Her bir pestisit için cihazın dedeksiyon limiti (IDL) ve Metot dedeksiyon limiti (EMDL) hesaplanmıştır. Matriksde hazırlanan kalibrasyon grafiklerinden elde edilen korelasyon katsayıları 0.99'dan yüksektir. Doğruluk için ortalama geri kazanımlar %75.39-121.95 arasında ve bağıl standart sapmalar (%RSD) %20'den düşüktür. Ayrıca kesinlik (gün içi tekrarlanabilirlik ve günler arası tekrar üretilebilirlik) için hesaplanan %RSD değerleri %10'dan düşük bulunmuştur. Geliştirilen metod basit, atığı az ve ekonomiktir. Kalıntı izleme programlarında kolaylıkla kullanılabileceği düşünülmektedir.

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Aksu P. 2007. Meyve ve sebzelerdeki pestisit kalıntılarının tayininde gaz kromatografisi/kütle spektrometresi (GC/MS) ile çoklu kalıntı analiz yönteminin geliştirilmesi. Doktora Tezi (yayınlanmamış), E.Ü. Fen Bilimleri Enstitüsü, İzmir, 389 s
Anastassiades M., Lehotay S.J., tajnbaher N. and Schenck F.J. 2003. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and dispersive solidphase extraction for the determination of pesticide residues in produce, Journal of AOAC International, 86 (2), 412-431.
Anonymous 2004. Guidance document on residue analytical methods, SANCO/825/00 rev. 7 17/03/2004.
Anonymous 2007. European Commissin DG SANCO, Method validation and quality control procedures for pesticide residues analysis in food and feed, No SANCO/2007/3131/31 October 2007.
Anonymous 2011. European Commissin DG SANCO, Method validation and quality control procedures for pesticide residues analysis in food and feed, No SANCO/2011/12495/01 January 2012.
Arrebola F. J., Martínez Vidal J. L., Mateu-Sánchez M. and Álvarez Castellόn F. J. 2003.
Determination of 81 multiclass pesticides in fresh foodstufs by a single injection analysis using gas chromotography-chemical ionization and electron ionization tandem mass spectrometry. Analytica Chimica Acta, 484, 167-180.
Balinova A., Mladenova R. and Shtereva D. 2007. Solid-phase extraction on sorbents of different retention mechanisms followed by determination by gas chromatographymass spectrometric and gas chromatography- electron capture detection of pesticide residues in crops. J. of Chromatography A, 1150, 136-144.
Caboni P., Sarais G., Angioni A., Garau V. L. and Cabras P. 2005. Fast and versalite multiresidue method for the analysis of botanical insecticides on fruits and vegetables by HPLC/DAD/MS. J Agric Food Chem., 53 (22), 8644-9.
Columé A., Cárdenas S., Gallego M. and Valcárcel M. 2000. Simplified method for the determination of clorinated fungicides and insecticides in fruits by gas chromatography. Journal of Chromatography A, 882, 193-203.
Díez C., Traag W. A., Zommer P., Marinero P. and Atienza J. 2006. Comparison of an acetonitrile extraction/partitioning and dispersive solid-phase extraction method with classical multi-residue methods for the extraction of herbicide residues in barley samples. Journal of Chromatography A, 1131, 11-23.
Erdik E., Obalı M., Yüksekışık N., Öktemer A., Pekel T. ve İhsanoğlu E. 2000. Denel organik kimya. A.Ü basımevi, Ankara, 805 s.
Garrido Frenich A., Martinez Vidal J. L., López López T., Cortés Aguado S. and Martínez Salvador I. 2004. Monitoring multi-class pesticide residues in fresh fruits and vegetables by liquid chromatography with tandem mass spectrometry. J. of Chromatography A, 1048, 199-206.
González-Rodríguez R. M., Otero Rial- R., Cancho-Grande B. and Simal-Gándara J. 2008. Occurance of fungicide and insecticide residues in trade samples of leafy vegetables. Food Chemistry, 107, 1342-1347.
Liu Z. M., Zang X. H., Liu W. H., Wang C. and Wang Z. 2009. Novel method for the determination of five carbamate pesticides in water samples by dispersive liquidliquid microextraction combined with high performance liquid chromatography. Chinese Chemical Letters, 20 (2) 213-216.
Masqué N., Marcé R. M. and Borrull F. 1998. Comparison of different sorbents for on-line solid-phase extraction of pesticides and phenolic compounds from natural water followed by liquid chromatography. Journal of Chromatography A, 793, 257-263.
Melo L.F.C., Collins C.H. and Jardim I.C.S.F. 2005. High-performance Liquid Chromatographic determination of pesticides in tomatoes using laboratory made NH2 and C18 solid-phase extraction materials. Journal of Chromatography A, 1073, 75-81.
Miliadis G. E., Tsiropoulos N. G. and Aplada Sarlis P.G. 1999. High-Performance Liquid Chromatographic determination of benzoylurea insecticides residues in grapes and wine using liquid and solid-phase extraction. J.Chromatogr A, 835, 113-20.
Obana H., Okihashi M., Akutsu K., Kitagawa Y. and Hori S. 2002. Determination of acetamiprid, imidacloprid and nitenpyram residues in vegetables and fruits by highperformance liquid chromatography with diode-array detection. J. Agric. Food Chem, 50, (16) 4464-4467.
Okihashi M., Kitagawa Y., Akutsu K., Obana H. and Tanaka Y. 2005. Rapid method for the determination of 180 pesticide residues in foods by gas chromatography/mass spectrometry and flame photometric detection. J. Pestic. Sci, 30 (4) 368-377.
Otero R.R., Grande C. and Gándara J.S. 2003. Multiresidue method for fourteen fungicides in white grapes by liquid-liquid and solid-phase extraction followed by liquid chromatography-diode array detection. Journal of Chromatography A, 992, 121-131.
Patil S.H., Banerjee K., Dasgupta S., Oulkar D.P., Patil S.B., Jadhav M.R., Savant R. H., Adsule P.G. and Deshmukh M.B. 2009. Multiresidue analysis of 83 pesticides and 12 dioxin-like polychlorinated biphenyls in wine by gas chromatography-time-offlight mass spectrometry. Journal of Chromatography A, 1216, 2307-2319.
Pizzutti I.R., Kok de A., Zenella R., Adaime M.B., Hiemstra M., Wickert C. and Prestes O.D. 2007. Method validation for the analysis of 169 pesticides in soya grain without clean up by liquid chromatography-tandem mass spectrometry using positive and negative electrospray ionization. Journal of Chromatography A, 1142, 123-36.
Simplício A.L. and Boas L.V. 1999. Validation of a solid-phase microextraction method for the determination of organophosphorus pesticides in fruits and fruit juice. Journal of Chromatography A, 883, 35-42.
Singh S. B., Foster G. D. and Khan S. U., 2007. Determination of thiophanate methyl and carbendazim residues in vegetable samples using microwave-assisted extraction. Journal of Chromatography A, 1148: 152157.
Shimelis O., Yang Y., Stenerson K., Kaneko T. and Ye M. 2007. Evaluation of a Solid- Phase Extraction dual-layer carbon/primary secondary amine for clean-up of fatty acid matrix components from food extracts in multiresidue pesticide analysis. Journal of Chromatography A, 1165, 18-25.
Synder L.R., Kırkland J.J. and Glajch J.L. 1997. Practical HPLC method development. John Willey&Sons, USA, 765 p.
Styarini D., Zuas O. and Hamim N. 2011. Validation and uncertainty estimation of analytical method for determination of benzene in beverages. Eurasion J Anal Chem 6(3), 159-172.
Temur C., Tiryaki O., Uzun O. and Başaran M. 2012. Adaptation and validation of QuEChERS method fort he analysis of Trifluralin in wind-eroded soil. J of Environmental Science and Health Part B 47, 842-850.
Thompson M., Ellison S.L.R. and Wood R. 2002. Harmonized guidelines for singlelaboratory validation of methods of analysis (IUPAC tecnical report). Pure Appl Chem, 74 (5) 835-855.
Tiryaki O. 2003. Nükleer ve Kromatografik tekniklerle pestisit kalıntılarının analiz edilmesi. VIII. Ulusal Nükleer Bilimler ve Teknolojileri Kongresi, 15-17 Ekim 2003, Kayseri, Bildiri Özetleri 15 s.
Tiryaki O., Baysoyu D., Seçer E. and Aydın G. 2008. Testing the stability of during sample perocessing for chlorprifos and malathion residue analysis in cucumber, including matrix effects. Bull Environ Contam Toxicol, 80, 38-43.
Tiryaki O. 2011. Pestisit kalıntı analizlerinde kalite kontrol (QC) ve kalite güvencesi (QA). Nobel yayın dağıtım, Ankara, 91-107.
Topuz S., Özhan G. and Alpertunga B. 2005. Simultaneous determination of various pesticides in fruit juices by HPLC-DAD. Food Control, 16, 87-92.
Vázquez P.P., Galera M.M., Frenich A.G. and Martínez Vidal J.L. 2000. Comparision of calibration methods with and without feature selection for the analysis of HPLC data. Analytical Sciences, 16, 49-55.
Yavuz O. ve Aksoy A. 2006. Örnek hazırlamada Katı Faz Ekstraksiyon metodu. F.Ü. Sağlık Bil. Der, 20, 259-269.